CN103480409B

CN103480409B - There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and method for hydrotreating hydrocarbon oil

Info

Publication number: CN103480409B
Application number: CN201210193602.4A
Authority: CN
Inventors: 杨清河; 曾双亲; 刘滨; 王奎; 任亮; 刘佳; 聂红; 李大东
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2012-06-12
Filing date: 2012-06-12
Publication date: 2016-01-13
Anticipated expiration: 2032-06-12
Also published as: CN103480409A

Abstract

The invention provides a kind of Catalysts and its preparation method and the application with hydrogenation catalyst effect, this catalyst contains carrier and load at least one group VIII metallic element on the carrier and at least one group vib metallic element, described group VIII metallic element and group vib metallic element are non-uniform Distribution along this catalyst radial section separately, wherein, along this catalyst radial section

Description

Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and hydrocarbon oil hydrotreating method

Technical Field

The invention relates to a catalyst with hydrogenation function, a preparation method and application thereof, and also relates to a hydrocarbon oil hydrotreating method.

Background

Besides sulfur and nitrogen, heavy oil also contains a large amount of metal impurities such as Ni, V, Fe, Ca and the like, as well as asphaltenes and colloids. During the hydrotreating process of such raw oil, these impurities may be adsorbed on the surface of the catalyst to cover active centers or deposited in the catalyst channels to block the channels, thereby causing the deactivation of the catalyst. Therefore, the metal-tolerant capacity and the carbon deposit resistance of the catalyst used in the heavy oil hydrotreating process directly affect the service life and the like of the catalyst.

US4760045 discloses a heavy oil hydrotreating catalyst comprising a porous refractory oxide support and supported thereon at least one active metal component having a hydrogenation catalytic action selected from the group consisting of groups VB, VIB and VIII of the periodic table of elements, wherein the metal component has a concentration distribution such that Cr satisfies the conditions of Cr distribution along the catalyst cross-section_l<Cr₂And R_l>R₂Wherein R is₁And R₂Respectively represent the distances r from the center of the cross section to the corresponding points₁And r₂Ratio to distance from center to outer surface of cross section, Cr₁And Cr₂Respectively represent the concentrations of the metal components at the corresponding points.

CN101376106B discloses a heavy oil hydrotreating catalyst, which comprises a carrier and an effective amount of at least one metal component selected from group VIII and at least one metal component selected from group VIB, wherein the concentration of the group VIII metal component is non-uniformly distributed along the radial section of the catalyst, wherein the ratio of the concentration of the metal component on the outer surface to the concentration of the metal component at the center is 0.1-0.85; the concentration of the VIB group metal component is uniformly distributed along the radial section of the catalyst, wherein the ratio of the concentration of the outer surface metal component to the concentration of the central metal component is 0.90-1.5. The carrier in the catalyst is alumina.

CN101462080A discloses a method for preparing a catalyst with non-uniform distribution of active metal components, which comprises introducing an effective amount of at least one metal component selected from VIII group and at least one metal component selected from VIB group on a carrier by adopting an impregnation method, wherein, the impregnation comprises the following steps: (1) sequentially mixing one or more acids selected from nitric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid, pimelic acid and adipic acid with at least one compound containing a metal component of a VIB group, at least one compound containing a metal component of a VIII group and water to form a solution, wherein the ratio of the number of moles of the acid to the sum of the number of moles of the compound comprising the group VIB metal component and the group VIII metal component is from 0.1 to 0.92, the amount of the water is such that the amount of the final solution by volume is 0.85 eta-1.1 eta, and eta is the water absorption rate of the carrier; (2) soaking the carrier in the mixed solution prepared in the step (1) at room temperature for 1-5 hours; (3) drying the impregnated carrier in the step (2) at the temperature of more than 60-160 ℃ for 2-10 hours, and roasting at the temperature of 400-600 ℃ for 2-5 hours.

Practical application shows that the heavy oil hydrotreating catalyst has better use stability in the heavy oil hydrotreating process.

However, as crude oil properties become worse, refineries have to process much poorer crude oils, and thus hydrogenation catalysts having higher catalytic activity, better catalytic stability and longer service life are urgently required.

Disclosure of Invention

The invention aims to provide a catalyst with hydrogenation catalysis effect and a preparation method thereof, wherein the catalyst shows higher catalytic activity, better catalytic stability and longer service life in the hydrogenation treatment of hydrocarbon oil (particularly heavy hydrocarbon oil).

The inventors of the present invention found in the course of research that a catalyst formed by preparing a carrier from a raw material containing at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, supporting a group VIII metal element and a group VIB metal element on the carrier, and distributing the group VIII metal element and the group VIB metal element in a "yolk" type distribution (i.e., the concentration of active metal at the center of the catalyst is higher than that at the outer surface of the catalyst) shows higher catalytic activity in the hydrotreating of hydrocarbon oil, particularly heavy hydrocarbon oil. Thus, the present invention has been completed.

The invention provides a catalyst with hydrogenation catalysis effect, which comprises a carrier, and at least one VIII group metal element and at least one VIB group metal element which are loaded on the carrier, wherein the VIII group metal element and the VIB group metal element are respectively non-uniformly distributed along the radial section of the catalyst, wherein along the radial section of the catalyst,

is the average concentration of the group VIII metal element at the outer surface of the catalyst;

is the average concentration of the group VIII metal element at the center of the catalyst;

is the average concentration of the group VIB metal element on the outer surface of the catalyst;

is the average concentration of the group VIB metal element at the center of the catalyst;

the carrier is hydrated alumina forming matter and is prepared from raw materials containing at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether.

In a second aspect of the present invention, there is provided a process for preparing a catalyst having a hydrocatalytic effect, which comprises supporting at least one group VIII metal element and at least one group VIB metal element on a carrier, said group VIII metal element and said group VIB metal element being substantially supported on said carrier in the form of salts, wherein said carrier is a hydrated alumina shaped body prepared by shaping a raw material comprising at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and drying the obtained shaped body at a temperature higher than 180 ℃ and not higher than 300 ℃.

A third aspect of the invention provides a catalyst prepared by the process of the invention.

A fourth aspect of the invention provides the use of a catalyst according to the invention in the hydroprocessing of hydrocarbon oils.

A fifth aspect of the present invention provides a process for hydrotreating a hydrocarbon oil, which comprises contacting a hydrocarbon oil with the catalyst of the present invention under hydrotreating conditions.

The catalyst according to the invention shows higher catalytic activity in the hydrodemetallization reaction of hydrocarbon oil (particularly heavy hydrocarbon oil). Moreover, when the catalyst of the present invention is used in a hydrodemetallization reaction of hydrocarbon oil (particularly heavy hydrocarbon oil), the removed metal tends to deposit at the center of the catalyst, so that the catalyst according to the present invention has a higher metal-holding capacity, and thus has higher stability and longer service life.

According to the preparation method of the catalyst with hydrogenation catalysis, the raw material containing at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether is molded, and the molded product prepared by drying the molded product at the temperature higher than 180 ℃ and not higher than 300 ℃ is used as a carrier, so that the catalyst with the active components (namely, the VIII group metal element and the VIB group metal element) distributed in a yolk shape can be prepared by adopting a conventional method in the field. I.e. the method according to the invention is simple and easy to implement.

Detailed Description

The invention provides a catalyst with hydrogenation catalysis effect, which comprises a carrier and at least one VIII group metal element and at least one VIB group metal element loaded on the carrier. The term "at least one" means one or two or more.

The catalyst of the invention takes VIII group metal elements and VIB group metal elements as active components with hydrogenation catalysis. The contents of the group VIII metal elements and the group VIB metal elements may be appropriately selected according to the specific application of the catalyst. For example, when the catalyst according to the present invention is used for hydrotreating of a hydrocarbon oil (particularly, a heavy hydrocarbon oil), the content of the carrier may be 70 to 95 wt%, preferably 75.5 to 93 wt%, based on the total amount of the catalyst; the content of the group VIII metal element may be 1 to 8% by weight, preferably 1 to 4.5% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 3 to 22 wt.%, preferably 5 to 20 wt.%, calculated as oxide.

According to the catalyst of the present invention, the group VIII metal element and the group VIB metal element may be various elements having a hydrogenation catalytic action commonly used in the art. Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten.

According to the catalyst of the present invention, the group VIII metal element and the group VIB metal element are substantially (i.e., mainly or substantially) supported on the carrier in the form of salts. That is, the group VIII metal element is supported on the carrier in the form of a salt containing the group VIII metal element, and the group VIB metal element is supported on the carrier in the form of a salt containing the group VIB metal element. That is, the group VIII metal element and the group VIB metal element are supported on the carrier substantially (i.e., mainly or substantially) in a non-oxide form.

According to the catalyst of the invention, the group VIII metal element and the group VIB metal element are non-uniformly distributed along the radial section of the catalyst, wherein, along the radial section of the catalyst,

is the average concentration of the group VIB metal element at the center of the catalyst.

Preferably, the catalyst is, in radial cross-section,

in the present invention, the distribution of the metal element along the radial cross section of the catalyst is measured using a scanning electron microscope and an energy spectrometer (i.e., SEM-EDX), and the ratio of the average concentration of the metal element at the outer surface of the catalyst particle to the average concentration at the center is calculated. Wherein the average concentration of the outer surface is the average value of the recording rate of 20 numerical points at the outer surface; the average concentration at the center is the average value of the 20-value point counting rates at the center point (note: the counting rate of each point along the radial direction of the carrier in the SEM-EDX characterization result corresponds to the metal content of the point, and the size of the counting rate reflects the metal content of the point but does not represent the real metal content of the point).

According to the catalyst, the carrier is hydrated alumina forming matter and is prepared from raw materials containing at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether.

According to the catalyst of the present invention, the feedstock contains at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, but no peptizing agent (e.g., alumina sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid).

According to the catalyst of the present invention, the composition of the raw material may be appropriately selected depending on the application of the catalyst. Generally, the total content of the cellulose ether may be from 0.5 to 8% by weight, preferably from 1 to 6% by weight, more preferably from 2 to 5% by weight, based on the total amount of the starting materials; the total content of the Y molecular sieve may be 0.5 to 55 wt%, preferably 1 to 50 wt%, more preferably 2 to 45 wt%; with Al₂O₃The total content of the hydrated alumina may be 37 to 98% by weight, preferably 44 to 97% by weight; more preferably 50 to 95 wt%. In the present invention, the hydrated alumina is Al when the total amount of the raw materials is calculated₂O₃And the feedstock does not include water introduced during the forming of the feedstock.

In the present invention, the cellulose ether refers to an ether derivative in which hydrogen atoms of at least some of hydroxyl groups in a cellulose molecule are substituted with one or more hydrocarbon groups, and the hydrocarbon groups may be the same or different. The hydrocarbyl group is selected from substituted hydrocarbyl and unsubstituted hydrocarbyl. The unsubstituted hydrocarbon group is preferably an alkyl group (e.g., C)₁-C₅Alkyl groups of (ii). In the present invention, C₁-C₅Specific examples of the alkyl group of (1) include C₁-C₅Straight chain alkyl of (2) and C₃-C₅The branched alkyl group of (a), may be, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and tert-pentyl. The substituted hydrocarbyl group may be, for example, an alkyl group substituted with a hydroxyl group or a carboxyl group (e.g., C)₁-C₅Alkyl substituted by hydroxy, C₁-C₅The alkyl group substituted with a carboxyl group) of (a), specific examples thereof may include, but are not limited to: hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethylCarboxyethyl and carboxypropyl.

The kind of the cellulose ether and the number of the substituents for substituting the hydrogen atoms on the hydroxyl groups in the cellulose molecule in the present invention are not particularly limited, and various cellulose ethers can be used. In particular, the cellulose ether may be selected from, but is not limited to: methyl cellulose, ethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and carboxymethyl hydroxyethyl cellulose. Preferably, the cellulose ether is selected from the group consisting of methylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.

In the present invention, the Y molecular sieve may be any of various Y molecular sieves commonly used in the art according to the shaped product of the present invention. For example, the Y molecular sieve may be selected from NaY molecular sieve, CaY molecular sieve, NH₄Y molecular sieve, HY molecular sieve, REY molecular sieve and ultrastable Y molecular sieve. Preferably, the Y molecular sieve is selected from NH₄Y molecular sieve, HY molecular sieve, REY molecular sieve and ultrastable Y molecular sieve.

In the present invention, the kind of the hydrated alumina is not particularly limited, and may be conventionally selected in the art. Preferably, the hydrated alumina is selected from the group consisting of boehmite, gibbsite, amorphous hydrated alumina and pseudoboehmite. More preferably, the hydrated alumina is pseudoboehmite.

According to the invention, the raw material may also contain at least one extrusion aid. The level of extrusion aid may be selected as is conventional in the art. In general, the total content of the extrusion aids may be from 0.1 to 8% by weight, preferably from 0.5 to 5% by weight, based on the total amount of the raw materials. The type of the extrusion aid is not particularly limited in the invention, and can be selected conventionally in the field. Preferably, the extrusion aid is starch (i.e., the feedstock also contains starch). The starch used as an extrusion aid may be starch from various sources commonly used in the art, for example: powder obtained by pulverizing plant seeds, such as sesbania powder.

According to the catalyst of the present invention, the support can be produced by preparing a molded body from the raw material and drying the molded body. The molded article can be produced by various methods commonly used in the art, and is not particularly limited. For example: the shaped bodies can be obtained by directly mixing at least one hydrated alumina, at least one cellulose ether and at least one Y molecular sieve with water and shaping the resulting mixture. According to the present invention, the amount of water used for preparing the mixture is not particularly limited as long as the amount of water is an amount that ensures uniform mixing of the various components.

The catalyst according to the present invention, the forming method is not particularly limited, and various forming methods commonly used in the art may be employed, for example: extrusion, spraying, spheronization, tableting or a combination thereof. In a preferred embodiment of the invention, the shaping is carried out by means of extrusion.

According to the catalyst of the invention, the support may have various shapes according to the specific use requirements, for example: spherical, bar, annular, clover, honeycomb, or butterfly.

According to the present invention, the conditions for drying the shaped body are not particularly limited, and may be selected conventionally in the art so that volatile components on the shaped body can be removed. For example: the temperature of the drying may be 60 ℃ or more and less than 350 ℃. Preferably, the drying is carried out at a temperature greater than 180 ℃ and not greater than 300 ℃ (e.g., 190-. More preferably, the temperature of the drying is 200-. According to the invention, the drying time can be properly selected according to the drying temperature, so that the volatile content in the finally obtained molded product meets the use requirement. Generally, the drying time may be 1 to 48 hours, preferably 2 to 24 hours.

According to the catalyst of the present invention, the carrier has good strength and absorption properties.

Specifically, the carrier has a radial crush strength loss rate (i.e., value) of 10% or less, and can even be 5% or less (e.g., 4% or less) after soaking.

In the present invention, the value used for evaluating the strength retention of the carrier is defined by the following formula:

δ = \frac{Q_{1} - Q_{2}}{Q_{1}} \times 100 %,

wherein Q is₁The radial crush strength, in N/mm, of the carrier that has not been soaked in water,

Q₂the radial crush strength in N/mm of the carrier after soaking in water for 30 minutes and drying at 120 ℃ for 4 hours.

Radial crush strength (i.e., Q) of a non-water-soaked support according to the catalyst of the present invention₁) Can be 12N/mm or more, even 15N/mm or more, and generally 15 to 30N/mm (e.g., 17 to 25N/mm).

In the present invention, the radial crush strength is measured by a method specified in RIPP25-90 described in "analytical methods for petrochemical engineering" (first edition 1990, ed. Yang Cui, Ltd.).

According to the catalyst of the present invention, the water absorption of the carrier is 0.4 to 1.5, generally 0.6 to 1.

In the present invention, the water absorption refers to a ratio of a weight change value of a dried carrier before and after being soaked in excess deionized water for 30 minutes to a weight of the dried carrier. The specific test method comprises the following steps: drying the carrier to be detected at 120 ℃ for 4 hours, then sieving by using a 40-mesh standard sieve, and weighing 20g of oversize material asSample to be tested (denoted as w)₁) The sample to be tested is soaked in 50g of deionized water for 30 minutes, after filtration, the solid phase is drained for 5 minutes, and the weight of the drained solid phase is then weighed (denoted as w)₂) The water absorption was calculated using the following formula:

the catalyst according to the invention may also contain at least one component capable of improving the catalytic properties of the catalyst, such as: phosphorus element. The content of the component capable of improving the catalytic performance of the catalyst is not particularly limited in the present invention, and may be conventionally selected in the art. Generally, the content of the component capable of improving the catalytic performance of the catalyst may be 0.1 to 10% by weight, preferably 0.5 to 5% by weight, in terms of oxide, based on the total amount of the catalyst.

The catalyst according to the invention can be prepared by the methods commonly used in the art for preparing active ingredients in a "yolk" type distribution. The inventors of the present invention found in the course of their research that when a support for supporting an active component having a hydrogenation catalytic action is prepared from a raw material comprising at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and the molded body is prepared by drying the molded body at a temperature higher than 180 ℃ and not higher than 300 ℃, a catalyst having an active component distributed in the form of "egg yolk" can be obtained by supporting the active component on the support using a conventional method.

Thus, according to a second aspect of the present invention, there is provided a process for preparing a catalyst having a hydrocatalytic effect, which comprises supporting at least one group VIII metal element and at least one group VIB metal element on a carrier, said group VIII metal element and said group VIB metal element being substantially supported on said carrier in the form of salts, wherein said carrier is a hydrated alumina shaped body prepared by shaping a starting material comprising at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and drying the shaped body obtained at a temperature higher than 180 ℃ and not higher than 300 ℃.

According to the method, the loading amounts of the VIII group metal element and the VIB group metal element on the carrier are determined so that the contents of the VIII group metal element and the VIB group metal element in the finally prepared catalyst can meet specific use requirements. For example, when the catalyst according to the present invention is used for hydrotreating hydrocarbon oils (particularly heavy hydrocarbon oils), the loading amounts of the group VIB metal element-containing compound and the group VIII metal element-containing compound on the carrier may be such that the carrier may be contained in an amount of 70 to 95 wt%, preferably 75.5 to 93 wt%, based on the total amount of the finally prepared catalyst; the content of the group VIII metal element may be 1 to 8% by weight, preferably 1 to 4.5% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 3 to 22 wt.%, preferably 5 to 20 wt.%, calculated as oxide.

According to the process of the invention, the group VIII metal element is preferably cobalt and/or nickel and the group VIB metal element is preferably molybdenum and/or tungsten.

According to the process of the invention, the group VIII metal element and the group VIB metal element are substantially (i.e. mainly or essentially) supported on the support in the form of salts. In other words, the group VIII metal element and the group VIB metal element are substantially (i.e., predominantly or substantially) supported on the carrier in a non-oxide form.

The group VIII and group VIB metallic elements may be supported on the support substantially in the form of salts (i.e. substantially in the form of non-oxides) in various ways commonly used in the art, for example: and (4) dipping. The impregnation may be a saturated impregnation or an excess impregnation. According to the method, the VIII group metal element and the VIB group metal element can be loaded on the carrier at the same time, or the VIII group metal element and the VIB group metal element can be loaded on the carrier in times.

In one embodiment of the invention, the manner in which the group VIII and group VIB metallic elements are supported on the support substantially in the form of salts (i.e. substantially in the form of non-oxides) comprises: impregnating the carrier with an aqueous solution containing at least one salt containing a group VIII metal element and at least one compound containing a group VIB metal element, and drying the impregnated carrier.

In another embodiment of the invention, the manner in which the group VIII and group VIB metallic elements are supported on the support substantially in the form of salts (i.e. substantially in the form of non-oxides) comprises: impregnating the carrier with an aqueous solution containing at least one salt containing a group VIII metal element, drying the impregnated carrier, impregnating the carrier loaded with the salt containing a group VIII metal element with an aqueous solution containing at least one compound containing a group VIB metal element, and drying the impregnated carrier.

In yet another embodiment of the present invention, the manner of supporting the group VIII metal element and the group VIB metal element on the support substantially in the form of salts (i.e., substantially in the form of non-oxides) comprises: impregnating the carrier with an aqueous solution containing at least one compound containing a group VIB metal element, drying the impregnated carrier, impregnating the carrier loaded with the compound containing the group VIB metal element with an aqueous solution containing at least one salt containing a group VIII metal element, and drying the impregnated carrier.

According to the present invention, the group VIII metal element-containing salt may be various group VIII metal element-containing water-soluble salts commonly used in the art, for example: the group VIII metal element-containing salt may be selected from water-soluble group VIII metal salts of inorganic acids, water-soluble group VIII metal salts of organic acids, and water-soluble salts formed by contacting a group VIII metal element-containing water-insoluble compound with an acid (e.g., phosphoric acid) and/or a base (e.g., aqueous ammonia) in water.

Specifically, the group VIII metal element-containing salt may be selected from, but is not limited to: cobalt nitrate, cobalt acetate, water-soluble salts of cobalt hydroxycarbonate in water with an acid (e.g., phosphoric acid) and/or a base (e.g., aqueous ammonia), cobalt chloride, water-soluble cobalt complexes, nickel nitrate, nickel acetate, water-soluble salts of nickel hydroxycarbonate in water with an acid (e.g., phosphoric acid) and/or a base (e.g., aqueous ammonia), nickel chloride, and water-soluble nickel complexes. The water-soluble cobalt complex may be, for example, cobalt ethylenediaminetetraacetate; the water-soluble nickel complex may be, for example, nickel citrate. Preferably, the group VIII metal element-containing salt is selected from the group consisting of cobalt nitrate, a water-soluble salt of cobalt hydroxycarbonate in water contacted with an acid (e.g., phosphoric acid) and/or a base (e.g., aqueous ammonia), a water-soluble salt of nickel hydroxycarbonate in water contacted with an acid (e.g., phosphoric acid) and/or a base (e.g., aqueous ammonia), and nickel nitrate.

According to the present invention, the kind of the group VIB metal element-containing compound is not particularly limited, and may be a group VIB metal element-containing water-soluble compound commonly used in the art, for example, a water-soluble group VIB metal salt of an inorganic acid, a water-soluble group VIB metal salt of an organic acid, a group VIB metal element-containing heteropoly acid salt, and a group VIB metal oxide, which are contacted with an acid (such as phosphoric acid) or a base in water to form a water-soluble compound.

Specifically, the group VIB metal element-containing compound may be selected from water-soluble salts of molybdic acid, water-soluble salts of paramolybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl ammonium metatungstate, phosphotungstic acid, phosphomolybdic acid, nickel phosphotungstate, cobalt phosphotungstate, nickel silicotungstate, cobalt silicotungstate, nickel phosphomolybdate, cobalt phosphomolybdate, nickel phosphomolybdotungstate, cobalt phosphomolybdotungstate, nickel silicomolybdotungstate, cobalt silicomolybdotungstate, and water-soluble compounds formed by contacting molybdenum oxide with phosphoric acid in water. In the present invention, the water-soluble salt of molybdic acid includes water-soluble metal salt of molybdic acid and ammonium molybdate; the water-soluble compound of paramolybdic acid includes a water-soluble metal salt of paramolybdic acid and ammonium paramolybdate. Preferably, the group VIB metal element-containing salt is selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, ammonium tungstate, and water-soluble compounds formed by contacting molybdenum oxide with phosphoric acid in water.

According to the method of the present invention, the concentration of the aqueous solution is not particularly limited as long as the content of the group VIII metal element and the group VIB metal element in the finally prepared catalyst can satisfy the use requirements (such as the requirements described above).

According to the process of the invention, the impregnated support obtained may be dried under conditions customary in the art, such as: the temperature can be 100-200 ℃ (such as 100-180 ℃), preferably 120-150 ℃; the time may be 1 to 15 hours, preferably 3 to 10 hours.

According to the method of the invention, the carrier is prepared by forming a raw material containing at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and drying the formed body at a temperature higher than 180 ℃ and not higher than 300 ℃ (such as 190-300 ℃). Preferably, the temperature of the drying is 200-.

According to the method of the present invention, the drying time may be appropriately selected according to the specific situation, so as to remove the volatile components on the carrier. For example, the drying time may be 1 to 48 hours, preferably 2 to 24 hours.

According to the process of the present invention, the feedstock comprises at least one hydrated alumina, at least one Y molecular sieve, and at least one cellulose ether, but no peptizing agent (e.g., alumina sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid, and trichloroacetic acid).

According to the process of the present invention, the composition of the raw material may be appropriately selected depending on the application of the catalyst. Generally, the total content of the cellulose ether may be 0.5 to 8% by weight, preferably 1 to 6% by weight, more preferably 0.5 to 8% by weight, based on the total amount of the raw materials2-5 wt%; the total content of the Y molecular sieve may be 0.5 to 55 wt%, preferably 1 to 50 wt%, more preferably 2 to 45 wt%; with Al₂O₃The total content of the hydrated alumina may be 37 to 98% by weight, preferably 44 to 97% by weight; more preferably 50 to 95 wt%.

The types of cellulose ether, the Y molecular sieve and the hydrated alumina according to the method of the present invention have been described in detail in the foregoing, and will not be described in detail herein.

According to the process of the present invention, the feedstock may also contain at least one extrusion aid. The level of extrusion aid may be selected as is conventional in the art. Preferably, the total content of the extrusion aid may be 0.1 to 8% by weight, preferably 0.5 to 5% by weight, based on the total amount of the raw materials. The type of the extrusion aid is not particularly limited in the invention, and can be selected conventionally in the field. Preferably, the extrusion aid is starch (i.e., the feedstock also contains starch). The starch used as an extrusion aid may be starch from various sources commonly used in the art, for example: powder obtained by pulverizing plant seeds, such as sesbania powder.

The process according to the invention is prepared by shaping a starting material comprising at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether and drying the shaped body obtained. The molded article can be produced by various methods commonly used in the art, and is not particularly limited. For example: the shaped bodies can be obtained by directly mixing at least one hydrated alumina, at least one cellulose ether and at least one Y molecular sieve with water and shaping the resulting mixture. According to the present invention, the amount of water used for preparing the mixture is not particularly limited as long as the amount of water is an amount that ensures uniform mixing of the various components.

According to the method of the present invention, the molding method is not particularly limited, and various molding methods commonly used in the art may be employed, for example: extrusion, spraying, spheronization, tableting or a combination thereof. In a preferred embodiment of the invention, the shaping is carried out by means of extrusion.

According to the method of the invention, the support can have various shapes according to the specific use requirements, for example: spherical, bar, annular, clover, honeycomb, or butterfly.

The process according to the invention may also comprise the introduction onto the support of at least one component capable of improving the catalytic properties of the finally prepared catalyst, such as: phosphorus element. The components may be introduced onto the support by prior to loading the group VIII and group VIB metal elements; the components can also be loaded on the carrier at the same time of loading the VIII group metal element and the VIB group metal element. The amount of the component capable of improving the performance of the catalyst to be incorporated may be conventionally selected in the art. Generally, the component capable of improving the performance of the catalyst is introduced in an amount such that the content of the component in the finally prepared catalyst may be 0.1 to 10% by weight, preferably 0.5 to 5% by weight, in terms of oxide.

According to the method of the present invention, the carrier has good absorption properties, high strength and strength retention. Generally, the carrier has a radial crush strength loss (i.e., value) of 10% or less, and can even be 5% or less (e.g., 4% or less) after soaking; radial crush strength (i.e., Q) of non-water soaked carrier₁) Can be more than 12N/mm, even more than 15N/mm, generally 15-30N/mm (e.g. 17-25N/mm); the water absorption of the carrier is 0.4 to 1.5, typically 0.6 to 1.

In the catalyst prepared by the method, the VIB group metal element and the VIII group metal element with hydrogenation catalysis are distributed in a yolk shape, and show higher activity in the hydrogenation treatment of hydrocarbon oil (particularly heavy hydrocarbon oil).

Thus, a third aspect of the invention provides a catalyst prepared by the process of the invention.

Prepared by the process of the inventionThe group VIII metal element and the group VIB metal element are non-uniformly distributed along the radial section of the catalyst, wherein, along the radial section of the catalyst,

Preferably, the catalyst is, in radial cross-section,

the catalyst according to the invention shows higher catalytic activity, better stability and longer service life in the hydrotreatment of hydrocarbon oil (especially heavy hydrocarbon oil).

Thus, the fourth aspect of the invention also provides the use of a catalyst according to the invention in the hydroprocessing of hydrocarbon oils.

In the present invention, the hydrocarbon oil may be any of various hydrocarbon feedstocks requiring hydrotreating, and is preferably any of various heavy hydrocarbon feedstocks requiring hydrodemetallization. Specifically, the hydrocarbon oil may be crude oil, atmospheric residue, and vacuum residue.

The method for hydrotreating a hydrocarbon oil according to the present invention is a method for hydrotreating a hydrocarbon oil with higher efficiency by contacting a hydrocarbon oil with the catalyst provided by the present invention, and the remaining conditions for the hydrotreating are not particularly limited and may be appropriately selected according to the properties of the hydrocarbon oil to be treated, according to conventional knowledge in the art. For example, when the hydrocarbon oil is a heavy hydrocarbon oil, the hydrotreating conditions may include: the temperature can be 300-450 ℃, preferably 330-400 ℃; the hydrogen partial pressure can be 5-20MPa, preferably 6-18 MPa; the volume space velocity of the hydrocarbon oil can be 0.1-3.0 hours^-1Preferably 0.15 to 2 hours^-1(ii) a The hydrogen to oil volume ratio may be 200-.

According to the hydrocarbon oil hydrotreating process of the present invention, the catalyst may be presulfided under conditions conventional in the art before use. The presulfiding conditions can be, for example, presulfiding with sulfur, hydrogen sulfide or a sulfur-containing feedstock in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃, either outside the reactor or in situ within the reactor.

The present invention will be described in detail below with reference to examples and comparative examples.

In the following examples and comparative examples, the radial crush strength of the carrier was measured by the method specified in RIPP 25-90.

In the following examples and comparative examples, the value of the carrier was determined by the following method: the radial crush strength (denoted Q) of the non-water-soaked carrier was determined by the method specified in RIPP25-90₁) (ii) a The support is placed in 50g of deionized water, soaked for 30 minutes and then filtered, the solid obtained is dried at 120 ℃ for 4 hours and the radial crush strength (denoted Q) of the dried solid is determined according to the method specified in RIPP25-90₂) The following formula is adopted to calculate the value,

δ = \frac{Q_{1} - Q_{2}}{Q_{1}} \times 100 % .

in the following examples and comparative examples, the water absorption of the carrier was measured by the following method: drying the carrier to be detected at 120 ℃ for 4 hours, then sieving the carrier by using a 40-mesh standard sieve, and weighing 20g of oversize materials as a sample to be detected (marked as w)₁) The sample to be tested is soaked in 50g of deionized water for 30 minutes, after filtration, the solid phase is drained for 5 minutes, and the weight of the drained solid phase is then weighed (denoted as w)₂) The water absorption was calculated using the following formula:

in the following examples and comparative examples, the dry content was determined by baking a sample to be tested at 600 ℃ for 4 hours.

In the following examples and comparative examples, the composition of the catalyst was determined by X-ray fluorescence spectroscopy (i.e., XRF).

In the following examples and comparative examples, the distribution of the metal element along the radial section of the catalyst was measured by SEM-EDX, and the ratio of the average concentration of the metal element at the outer surface to the average concentration at the center of the catalyst particle was calculated. Wherein the average concentration of the outer surface is the average value of the recording rate of 20 numerical points at the outer surface; the average concentration at the center is the average value of the 20-value point counting rates at the center point (note: the counting rate of each point along the radial direction of the carrier in the SEM-EDX characterization result corresponds to the metal content of the point, and the size of the counting rate reflects the metal content of the point but does not represent the real metal content of the point).

Examples 1 to 8 serve to illustrate the catalyst according to the invention and the method for its preparation.

Example 1

(1) 100.0g of pseudo-boehmite powder (purchased from China petrochemical catalyst Changling division, dry basis content of 69.5 wt%), 4.0g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd.), 3.0g of sesbania powder, 20.0g of ultrastable Y molecular sieve (purchased from China petrochemical catalyst Changling division, cell constant of 69.5 wt.%), and a solventA dry content of 95 wt.% Na₂O content 0.05 wt.%) and 85g of deionized water. The resulting mixture was fed into an extruder and extruded to obtain wet strands. The extruded wet strands were placed in an oven and dried at 200 ℃ for 6 hours, thereby obtaining a carrier in the catalyst according to the present invention. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) 0.47 g of basic nickel carbonate (NiO content of 51 percent by weight), 1.20 g of molybdenum oxide and 0.23 g of phosphoric acid are dissolved in water to prepare 60mL of solution; the resulting solution was impregnated with 19.8g of the carrier (diameter 1.1mm, particle length 2 to 5mm, dry content 72.3% by weight) prepared in step (1) for 4 hours. After filtration, the resulting solid product was dried at 120 ℃ for 4 hours to obtain catalyst B1. The composition of the catalyst was determined by XRF and the results are shown in table 2.

Comparative example 1

(1) A carrier was prepared in the same manner as in example 1, except that methylcellulose was not used, but concentrated nitric acid of 2.5mL was used, and the extruded wet strip was dried at 200 ℃ for 6 hours, followed by firing at 600 ℃ for 4 hours, to thereby obtain a carrier. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) 0.47 grams of basic nickel carbonate (same as in example 1), 1.20 grams of molybdenum oxide, and 0.23 grams of phosphoric acid were dissolved in water to make a 60mL solution. The resulting solution was impregnated with 14.3g of the carrier (diameter 1.1mm, particle length 2 to 5 mm) prepared in step (1) for 1 hour. After filtration, the resulting solid product was dried at 120 ℃ for 4 hours to obtain catalyst A1. The composition of the catalyst was determined by XRF and the results are given in table 2.

Comparative example 2

(1) The carrier was prepared in the same manner as in comparative example 1, except that calcination was not carried out at 600 ℃ to obtain a carrier. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) The catalyst was prepared in the same manner as in comparative example 1, except that the carrier was the one prepared in step (1) of comparative example 2, and the dissolution and structural collapse of the carrier occurred during the impregnation, and the obtained catalyst a2 could not be used as a shaped catalyst.

Comparative example 3

A carrier and a catalyst were prepared in the same manner as in example 1, except that, in step (1), the extruded wet strip was placed in an oven and dried at 180 ℃ for 6 hours, thereby obtaining a carrier. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1. The catalyst obtained is denoted A3. The composition of the catalyst was determined by XRF and the results are given in table 2.

Comparative example 4

A carrier and a catalyst were prepared in the same manner as in example 1, except that, in step (1), the extruded wet strip was placed in an oven, dried at 200 ℃ for 6 hours, and then calcined at 500 ℃ for 3 hours, thereby obtaining a carrier. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1. The catalyst obtained is denoted A4. The composition of the catalyst was determined by XRF and the results are given in table 2.

Comparative example 5

A carrier and a catalyst were prepared in the same manner as in example 1, except that in the step (2), the obtained solid product was dried at 120 ℃ for 4 hours, followed by calcination at 500 ℃ for 3 hours, to thereby obtain a catalyst, which was designated as A5. The composition of the catalyst was determined by XRF and the results are given in table 2.

Example 2

(1) 2000mL of aluminum sulfate solution with the concentration of 48g/L and sodium metaaluminate solution (the content of alumina is 200g/L, the caustic coefficient is 1.58) are added into a 2L reaction tank in a cocurrent mode for precipitation reaction, the reaction temperature is 50 ℃, the pH value is 6.0, and the reaction retention time is 15 minutes; the obtained slurry was filtered with a vacuum filter, and after completion of the filtration, 20L of deionized water (40. + -. 5 ℃ C.) was additionally added to the filter cake to wash the filter cake for about 60 minutes. Adding the washed filter cake into 1.5L of deionized water, stirring to obtain slurry, pumping the slurry into a spray dryer for drying, controlling the outlet temperature of the spray dryer within the range of 100-110 ℃, and drying the material for 2 minutes to obtain the hydrated alumina, wherein the content of the alumina is 63 weight percent, and the alumina is determined to be amorphous by XRD analysis.

(2) 50.0g of pseudo-boehmite powder(69.5 wt% dry basis, available from China petrochemical catalyst ChangLing division), 50.0g of the amorphous hydrated alumina prepared in step (1), 2.0g of methylcellulose (available from Zhejiang Haishi chemical Co., Ltd.), 3.0g of hydroxyethylmethylcellulose (available from Shanghai Hui Guanghu Fine chemical Co., Ltd.), and 5.0g of a molecular sieve (available from China petrochemical Qilu catalyst division, having a unit cell constant of 69.0 g)94% by weight on a dry basis, Na₂0.31 wt.% O, 23.5 wt.% rare earth, calculated as oxide) and 92g of deionized water. The resulting mixture was fed into an extruder and extruded to obtain wet strands. The obtained wet strip was placed in an oven and dried at 220 ℃ for 6 hours, thereby obtaining a carrier in the catalyst according to the present invention. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(3) 1.18 g of basic nickel carbonate (NiO content of 51 wt%), 3.00 g of molybdenum oxide and 0.68 g of phosphoric acid were dissolved in water to prepare a 60mL solution. The resulting solution was impregnated with 19.4g of the carrier (diameter 1.1mm, particle length 2 to 5mm, dry content 73.7% by weight) prepared in step (2) for 4 hours. After filtration, the resulting solid was dried at 120 ℃ for 4 hours to obtain catalyst B2. The composition of the catalyst was determined by XRF and the results are given in table 2.

Example 3

(1) 60.0g of pseudo-boehmite (purchased from China petrochemical catalyst Long-green division, with a dry content of 69.5 wt%), 40.0g of gibbsite (purchased from Guangxi Pingguo aluminum, with a dry content of 64.5 wt%), 1.0g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd.), 2.0g of hydroxypropyl methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd.), 3.0g of sesbania powder, and 30.0g of NaY molecular sieve (purchased from China petrochemical Qilu catalyst division, with a cell constant of 69.0 g96 wt.% dry basis) and 120g of deionized water were stirred well. The resulting mixture was fed into an extruder and extruded to obtain wet strands. The obtained wet strip was placed in an oven and dried at 210 ℃ for 12 hours to obtain a carrier in the catalyst of the present invention. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) 0.34 g of basic cobalt carbonate (with a CoO content of 70 wt%), 1.20 g of molybdenum oxide and 0.23 g of phosphoric acid were dissolved in water to prepare a 60mL solution. The resulting solution was impregnated with 20.8g of the carrier (diameter 1.1mm, particle length 2 to 5mm, dry content 73.7% by weight) prepared in step (1) for 1 hour. After filtration, the obtained carrier was dried at 100 ℃ for 6 hours to obtain catalyst B3 of the present invention. The composition of the catalyst was determined by XRF and the results are given in table 2.

Example 4

(1) 100.0g of pseudoboehmite SB powder (purchased from Sasol company, dry content: 75.0 wt%), 3.0g of hydroxyethyl methyl cellulose (purchased from Shanghai Hui Guanghu Fine chemical Co., Ltd.), and 67.0gHY molecular sieve (purchased from China petrochemical Qilu catalyst division, cell constant: Sasol Co., Ltd.)92% by weight on a dry basis) and 150g of deionized water were stirred well. The resulting mixture was fed into an extruder and extruded to obtain wet strands. The obtained wet strip was placed in an oven and dried at 300 ℃ for 2 hours, thereby obtaining a carrier in the catalyst according to the present invention. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) 2.71 g of nickel nitrate (Ni (NO)₃)₂·6H₂O) and 4.11 g ammonium metatungstate ((NH)₄)₆W₇O₂₄·4H₂O) is dissolved in water and preparedA solution of 13.5mL was prepared. The resulting solution was impregnated with 18.5g of the carrier (diameter 1.1mm, particle length 2 to 5mm, dry content 77.5% by weight) prepared in step (1) for 1 hour. The resulting solid product was dried at 150 ℃ for 2 hours to obtain catalyst B4 of the present invention. The composition of the catalyst was determined by XRF and the results are given in table 2.

Comparative example 6

A carrier and a catalyst were prepared in the same manner as in example 4, except that, in step (1), the obtained wet strip was placed in an oven and dried at 330 ℃ for 2 hours, thereby obtaining a carrier, the radial crush strength, the water absorption rate and the values of which are listed in table 1. The catalyst obtained is denoted A6. The composition of the catalyst was determined by XRF and the results are given in table 2.

Example 5

(1) 100.0g of pseudo-boehmite SB powder (purchased from Sasol company, dry content: 75.0 wt%), 3.0g of hydroxyethyl methyl cellulose (purchased from Shanghai Hui Guang Fine chemical Co., Ltd.), 2.0g of hydroxypropyl methyl cellulose (purchased from Shanghai Hui Guang Fine chemical Co., Ltd.), 3.0g of sesbania powder, 20.0g of NaY molecular sieve (purchased from China petrochemical Qilu catalyst division, cell constant: Sago, Ltd.)96 wt.% dry basis) was mixed with 115g of deionized water. The resulting mixture was fed into an extruder and extruded to obtain wet strands. The obtained wet strip was placed in an oven and dried at 250 ℃ for 4 hours, thereby obtaining a carrier in the catalyst according to the present invention. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) 0.78 g of basic nickel carbonate (NiO content: 51 wt%), 2.00 g of molybdenum oxide and 0.38 g of phosphoric acid were dissolved in water to prepare a 60mL solution. The resulting solution was impregnated with 19.7g of the carrier (diameter 1.1mm, particle length 2 to 5mm, dry content 72.5% by weight) prepared in step (1) for 4 hours. After filtration, the obtained solid was dried at 180 ℃ for 2 hours to obtain catalyst B5 of the present invention. The composition of the catalyst was determined by XRF and the results are given in table 2.

Example 6

(1) 100.0g of pseudo-boehmite (purchased from Shandong tobacco stage Henghui chemical Co., Ltd., dry basis content of 71.0 wt%), 5.0g of hydroxypropyl methylcellulose (purchased from Shanghai Hei Guang Fine chemical Co., Ltd.), 3.0g of sesbania powder, 35.0g of NH₄Y molecular sieve (purchased from Qilu catalyst division, petrochemical, China, having a unit cell constant of91% by weight on a dry basis) was mixed with 110g of deionized water. The resulting mixture was fed into an extruder and extruded to obtain wet strands. The obtained wet strip was placed in an oven and dried at 190 ℃ for 4 hours, thereby obtaining a carrier in the catalyst according to the present invention. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) 1.76 g of basic nickel carbonate (NiO content of 51 wt%), 4.50 g of molybdenum oxide and 0.84 g of phosphoric acid were dissolved in water to prepare a 60mL solution. The obtained solution was impregnated with 19.8g of the carrier (diameter 1.1mm, particle length 2 to 5mm, dry content 72.2% by weight) obtained in step (1) for 4 hours. After filtration, the obtained solid product was dried at 160 ℃ for 4 hours to obtain catalyst B6 of the present invention. The composition of the catalyst was determined by XRF and the results are given in table 2.

Example 7

(1) A carrier was prepared in the same manner as in example 2, except that the content of methyl cellulose was 2.0g and the content of hydroxyethyl methyl cellulose was 5.0g, to obtain a carrier in the catalyst of the present invention. The radial crush strength, water absorption and values of the obtained carrier were measured, and the results are listed in table 1.

(2) A catalyst was prepared in the same manner as in example 2, except that the carrier was the one prepared in the step (1) of example 7, and the resulting catalyst was designated as B7. The composition of the catalyst was determined by XRF and the results are given in table 2.

TABLE 1

Numbering	Crush strength (N/mm)	Water absorption (%)	δ value (%)
				Example 1	23.4	0.86	3.1
Comparative example 1	19.1	0.89	3.3
				Comparative example 2	16.5	0.64	64.2
Comparative example 3	22.5	0.85	3.5
				Comparative example 4	23.6	0.88	3.1
Comparative example 5	23.7	0.86	3.1
				Example 2	19.8	0.70	2.5
Example 3	17.5	0.85	3.5
				Example 4	20.5	0.73	2.8
Comparative example 6	20.7	0.74	2.7
				Example 5	20.6	0.62	2.6
Example 6	19.9	0.73	2.7
				Example 7	20.2	0.69	2.4

The results in table 1 show that the support in the catalyst according to the present invention has good strength retention, high crush strength even after soaking in water.

TABLE 2

Examples 8 to 14 are for explaining the catalyst of the present invention and its application and a hydrocarbon oil hydrotreating process.

Examples 8 to 14

The catalysts prepared in examples 1 to 7 were evaluated using vacuum residue as a raw material, and the properties of the raw material oil of vacuum residue are shown in Table 3. The evaluation was carried out in a magnetic stirring autoclave apparatus.

The reaction conditions include: the mass ratio of the solvent to the oil is 0.05, the reaction temperature is 400 ℃, the initial reaction pressure of hydrogen is 8MPa, and the sampling analysis is carried out after the reaction is carried out for 6 hours. And (3) measuring the contents of nickel and vanadium in the oil generated by the reaction by adopting a plasma emission spectroscopy (AES/ICP) method. The demetallization rate was calculated by the following formula and the results are listed in table 4.

The distribution of vanadium deposited on the catalyst after the reaction was characterized on a radial section of the catalyst by SEM-EDX and the ratio (V) of the average concentration of vanadium on the outer surface of the catalyst to the average concentration at the center of the catalyst was calculated_{Outer surface}/V_{Center of a ship}) The results are listed in table 4.

Comparative examples 7 to 11

The performance of the catalysts prepared in comparative examples 1 and 3 to 6 was evaluated in the same manner as in examples 8 to 14, and the results are shown in Table 4.

TABLE 3

Density (20 ℃ C.) (g. cm^-3）	1.04
		Carbon residue (wt%)	25.68
Sulfur content (wt%)	7.23
		Nickel content (wppm)	73.9
Vanadium content (wppm)	183.4

TABLE 4

Example numbering	Catalyst numbering	Total metal removal rate (%)	V_{Outer surface}/V_{Center of a ship}
				Example 8	B1	78	0.51
Comparative example 7	A1	68	1.62
				Comparative example 8	A3	66	1.08
Comparative example 9	A4	67	1.27
				Comparative example 10	A5	69	1.17
Example 9	B2	90	0.43
				Example 10	B3	75	0.55
Example 11	B4	91	0.61
				Comparative example 11	A6	68	1.67
Example 12	B5	85	0.36
				Example 13	B6	90	0.65
Example 14	B7	89	0.64

The results in table 4 show that the catalyst according to the invention has a higher hydrodemetallization activity. Also, when the catalyst according to the present invention is used in a hydrodemetallization reaction of heavy hydrocarbon oil, the removed metals tend to deposit at the center of the catalyst, so that the catalyst according to the present invention has a higher metal-containing capacity, and thus the catalyst according to the present invention has better stability and longer service life.

Claims

1. A catalyst with hydrogenation catalysis effect comprises a carrier, and at least one VIII group metal element and at least one VIB group metal element which are loaded on the carrier, wherein the VIII group metal element and the VIB group metal element are respectively non-uniformly distributed along the radial section of the catalyst, wherein, along the radial section of the catalyst,

the carrier is a hydrated alumina forming product and is prepared from a raw material,

the raw material consists of at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, wherein the total content of the cellulose ether is 0.5-8 wt%, the total content of the Y molecular sieve is 0.5-55 wt%, and Al is used as the total content of the raw material₂O₃The total content of the hydrated alumina is 37-98 wt%, or

The raw material consists of at least one hydrated alumina, at least one Y molecular sieve, at least one cellulose ether and at least one extrusion aid, wherein the total content of the cellulose ether is 0.5-8 wt%, the total content of the Y molecular sieve is 0.5-55 wt%, and the Al is used as the total amount of the raw material₂O₃The total content of the hydrated alumina is 37-98 wt%, and the content of the extrusion aid is 0.1-8 wt%.

2. The catalyst according to claim 1, wherein, along a radial cross section of the catalyst,

3. the catalyst according to claim 1, wherein the carrier is present in an amount of 70 to 95 wt%, calculated as oxides, of the group VIII metal element in an amount of 1 to 8 wt%, and the group VIB metal element in an amount of 3 to 22 wt%, based on the total amount of the catalyst.

4. The catalyst according to claim 1, wherein the carrier is produced by molding the raw material and drying the molded product.

5. The catalyst of claim 4, wherein the temperature of the drying is greater than 180 ℃ and not greater than 300 ℃.

6. The catalyst of claim 5, wherein the drying temperature is 200-260 ℃.

7. The catalyst of claim 1 or 4, wherein the total content of the cellulose ether is 1-6 wt%, the total content of the Y molecular sieve is 1-50 wt%, based on the total amount of the raw materials, and Al is used as Al₂O₃The total content of the hydrated alumina is 44 to 97 wt%.

8. The catalyst of claim 7, wherein the total cellulose ether content is from 2 to 5 wt%, the total Y molecular sieve content is from 2 to 45 wt%, based on the total amount of the starting materials, expressed as Al₂O₃The total content of the hydrated alumina is 50 to 95% by weight.

9. The catalyst of claim 1 or 4, wherein the cellulose ether is selected from the group consisting of methylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.

10. The catalyst of claim 1 or 4, wherein the Y molecular sieve is selected from NaY molecular sieve, CaY molecular sieve, NH₄Y molecular sieve, HY molecular sieve, REY molecular sieve and ultrastable Y molecular sieve;

the hydrated alumina is selected from the group consisting of boehmite, gibbsite, amorphous hydrated alumina, and pseudoboehmite.

11. The catalyst according to any one of claims 1, 3 and 4, wherein the water absorption of the carrier is 0.4-1.5, the value is 10% or less, and Q is₁Is more than 12N/mm, and the grain size is less than 12N/mm,

wherein,

δ = \frac{Q_{1} - Q_{2}}{Q_{1}} \times 100 %,

Q₁the radial crush strength, in N/mm, of the carrier that has not been soaked in water,

12. The catalyst of claim 11, wherein the carrier has a water absorption of 0.6-1, a value of 5% or less, Q₁Is 15-30N/mm.

13. The catalyst according to any one of claims 1-3, wherein the group VIII metal element is cobalt and/or nickel and the group VIB metal is molybdenum and/or tungsten.

14. The catalyst according to claim 1, wherein the extrusion aid is present in an amount of 0.5 to 5 wt.%, based on the total amount of the feedstock.

15. The catalyst of claim 1 or 14, wherein the extrusion aid is starch.

16. The catalyst of claim 1 or 14, wherein the extrusion aid is sesbania powder.

17. A process for preparing a catalyst having a hydrocatalytic effect, which comprises supporting at least one group VIII metal element and at least one group VIB metal element on a carrier, said group VIII metal element and said group VIB metal element being supported on said carrier substantially in the form of salts, characterized in that said carrier is a hydrated alumina shaped body, which is obtained by shaping a starting material and drying the obtained shaped body at a temperature higher than 180 ℃ and not higher than 300 ℃,

18. The method as claimed in claim 17, wherein the drying temperature is 200-260 ℃.

19. The process of claim 17, wherein the total cellulose ether content is from 1 to 6 weight percent, the total Y molecular sieve content is from 1 to 50 weight percent, based on the total amount of the starting material, as Al₂O₃The total content of the hydrated alumina is 44 to 97 wt%.

20. The process of claim 19, wherein the total cellulose ether content is from 2 to 5 weight percent, the total Y molecular sieve content is from 2 to 45 weight percent, based on the total amount of the starting material, as Al₂O₃The total content of the hydrated alumina is 50 to 95% by weight.

21. The method of any one of claims 17, 19 and 20, wherein the cellulose ether is selected from the group consisting of methylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.

22. The method of any one of claims 17, 19 and 20, wherein the Y molecular sieve is selected from NaY molecular sieve, CaY molecular sieve, NH₄Y molecular sieve, HY molecular sieve, REY molecular sieve and ultrastable Y molecular sieve;

23. The process according to claim 17, wherein the loading amounts of the group VIB and group VIII metal elements on the carrier are such that the carrier is in the range of 70 to 95 wt.%, the group VIII metal element is in the range of 1 to 8 wt.% and the group VIB metal element is in the range of 3 to 22 wt.%, calculated as oxide, based on the total amount of the finally prepared catalyst.

24. The process according to claim 17, wherein the support is loaded with at least one group VIII metal element and at least one group VIB metal element by impregnation.

25. The method of claim 24, further comprising drying the impregnated support under conditions comprising: the temperature is 100-200 ℃ and the time is 1-15 hours.

26. The method according to any one of claims 17, 23 and 24, wherein the group VIII metal element is cobalt and/or nickel and the group VIB metal is molybdenum and/or tungsten.

27. The method according to claim 17, wherein the extrusion aid is present in an amount of 0.5-5 wt.%, based on the total amount of the feedstock.

28. The method of claim 17 or 27, wherein the extrusion aid is starch.

29. The method of claim 17 or 27, wherein the extrusion aid is sesbania powder.

30. A catalyst prepared by the process of any one of claims 17 to 29.

31. Use of a catalyst according to any one of claims 1 to 16 and 30 in the hydroprocessing of hydrocarbon oils.

32. A process for hydrotreating a hydrocarbon oil, which process comprises contacting the hydrocarbon oil under hydrotreating conditions with the catalyst of any one of claims 1-16 and 30.

33. The method of claim 32, wherein the hydrocarbon oil is one or more of crude oil, atmospheric resid, and vacuum resid.